JP2006257238A - Organic electroluminescent device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic platinum complex having good light emission properties (luminance, quantum efficiency, driving voltage), durability, and vapor deposition properties, and a light-emitting device containing the same. <P>SOLUTION: An organic electroluminescent device comprises an organic layer containing at least one compound represented by formula (I). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a platinum complex and an organic electroluminescent element (element).

In recent organic EL device development, various studies on improving external quantum efficiency have been conducted, and among them, devices containing phosphorescent materials using heavy metals such as iridium and platinum have achieved high efficiency and are attracting attention. .
In the development of a light emitting material using platinum, an example in which an aryl group is connected by an ether bond has been reported (for example, see Non-Patent Document 1). This platinum complex has a feature that the emission wavelength can be shortened from the conventionally reported tetradentate platinum complex such as octaethylporphyrin platinum complex (for example, see Patent Documents 1 and 2). Listed as a feature.
However, the platinum complex described in Non-Patent Document 1 has a problem that light emission at room temperature is extremely weak. In addition, when the remaining monodentate ligand uses a halogen atom such as a chlorine atom, the light emitting material containing it has low durability of the device, and its improvement has been desired.
US Pat. No. 6,303,238 B1 US Pat. No. 6,653,564B1 “Journal of Organometallic Chemistry”, 2004, 689, p. 2888-2899.

  An object of the present invention is to provide a platinum complex having good light emission characteristics (luminance, quantum yield, driving voltage), durability, and vapor deposition, and an element including the same.

In view of the above circumstances, the present inventors have conducted intensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein the organic layer contains at least one compound represented by the following general formula (I). An organic electroluminescent element.

[Wherein, Q ₁ represents an atomic group necessary for forming an unsaturated ring together with a carbon atom. Q ₂ and Q ₃ each independently represents an atomic group necessary for forming an unsaturated ring together with a nitrogen atom. X represents a partial structure containing an atom that is covalently bonded to a platinum atom. A ₁ represents a linking group, and B ₁ , B ₂ and B ₃ each independently represent a linking group or a single bond. However, when X represents a substituted or unsubstituted aryl group, both B ₁ and B ₃ are not a single bond. m and n each independently represents 0 or 1. However, m and n are not both 1. When m or n is 0, X represents an unsaturated ring formed with Q ₂ and a nitrogen atom, or an unsaturated ring formed with Q ₃ and a nitrogen atom, and X is not bonded. To do. ]

<2> The organic electroluminescence device according to <1>, wherein the general formula (I) is represented by the following general formula (II).

[Wherein, R ₁ , R ₂ and R ₃ each independently represents a substituent. p _1, p ₂ and p ₃ each independently represent an integer of 0-3. _{A 1, B 1, B 2} , B 3, m, n and X have the same meanings as _{A 1, B 1, B 2} , B 3, m, n and X in the general formula (I). ]

<3> The organic electroluminescent element as described in <1> above, wherein the general formula (I) is represented by the following general formula (III).

[Wherein R ₁ , R ₂ , R ₃ , p ₁ , p ₂ and p ₃ represent the same meaning in R ₁ , R ₂ , R ₃ , p ₁ , p ₂ and p ₃ in the general formula (II) . _{A 1, B 2, B 3} , m, n and X have the same meanings as _{A 1, B 2, B 3} , m, n and X in the general formula (I). ]

<4> The organic electroluminescence device according to <1>, wherein the general formula (I) is represented by the following general formula (IV).

[Wherein, A ₁ and B ₁ represent the same meaning as A ₁ and B ₁ in formula (I). _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). ]

<5> The organic electroluminescence device according to <1>, wherein the general formula (I) is represented by the following general formula (V).

[Wherein, A ₁ represents the same meaning as A ₁ in formula (I). _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). ]

<6> The organic electroluminescent element as described in <1> above, wherein the general formula (I) is represented by the following general formula (VI).

[Wherein A ₁ , B ₁ , B ₂ , B ₃ , m, n and X have the same meaning as A ₁ , B ₁ , B ₂ , B ₃ , m, n and X in the general formula (I) To express. _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). ]

  According to the present invention, it is possible to provide a platinum complex having excellent light emission characteristics (luminance, quantum yield, drive voltage), durability, and vapor deposition properties, and a light emitting device including the same.

The organic electroluminescent element of the present invention has at least one organic layer including a light emitting layer between a pair of electrodes, and is also referred to as a compound represented by the general formula (I) (hereinafter also referred to as “the compound of the present invention”). ) In the organic layer.
By adopting the above-described structure, that is, by containing the compound of the present invention having good light emission characteristics (brightness, quantum yield, driving voltage), durability, and vapor deposition in the organic layer, the light emission characteristics (brightness, quantum yield) are obtained. Rate, driving voltage), durability, and an organic electroluminescence device having excellent effects in vapor deposition can be obtained.
Hereinafter, the compound represented by the general formula (I) will be described.

In the general formula (I), Q ₁ represents an atomic group necessary for forming an unsaturated ring together with a carbon atom. Q ₂ and Q ₃ each independently represents an atomic group necessary for forming an unsaturated ring together with a nitrogen atom.
The atomic group is not particularly limited, but an atomic group selected from atoms independently selected from carbon, nitrogen, silicon, sulfur, oxygen, germanium, and phosphorus is preferable. The bond between the atoms forming the unsaturated ring may be any combination of a single bond, a double bond and a triple bond as long as it contains at least one unsaturated bond in the ring.
Q ₁ , Q ₂ and Q ₃ are preferably each independently formed from carbon, nitrogen, silicon, sulfur and oxygen, and more preferably from carbon, nitrogen and silicon. More preferably, it is formed by a carbon or nitrogen atom, and particularly preferably, Q ₁ , Q ₂ and Q ₃ are formed by carbon, and the unsaturated ring formed together with Q ₁ and the carbon atom is substituted benzene. In this case, the unsaturated ring formed together with Q ₂ or Q ₃ and the nitrogen atom independently forms a substituted pyridine ring.
In the atomic group constituting Q ₁ , Q ₂ , and Q ₃ , when further substitutable, they may each independently have a substituent. These substituents may be the same or different.

  Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl. , N-octyl, n-decyl, n-hexadecyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, such as cyclopropyl, Cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as vinyl, allyl, 2-butenyl, 3-pentenyl and the like), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, Preferably 2 to 10 carbon atoms, such as propargyl and 3-pentynyl in.),

An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl and the like), amino. Group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc. An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc. An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like, and heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably ) Has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, and the like.

An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 1 to 20, particularly preferably 1 to 10 carbon atoms, for example, acetoxy, benzoyloxy An acylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). ,

An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group ( Preferably it has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino, etc., and a sulfonylamino group (preferably 1 to 1 carbon atoms). 30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably C0-30, more preferably) Has 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms. Amoiru, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.),

A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like), alkylthio. A group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably having 6 to 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, and a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 carbon atom). -20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolyl Oh, 2-benzoxazolyl thio, and 2-benzthiazolylthio the like.),

A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), a sulfinyl group (preferably having 1 carbon atom). To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido groups (preferably 1 to 30 carbon atoms, more preferably C1-C20, Most preferably, it is C1-C12, for example, a ureido, methylureido, phenylureido etc. are mentioned), phosphoric acid amide groups (preferably C1-C30, more preferably carbon number) 1 to 20, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide That.), Hydroxy group, a mercapto group, a halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or more preferably fluorine atom.)

Cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, As, for example, nitrogen atom, oxygen atom, sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl), silyloxy group (Preferably 3 to 40 carbon atoms, more preferably 3 to 3 carbon atoms. , Particularly preferably 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted.

In the general formula (I), A ₁ represents a linking group. The linking group is not particularly limited, but is particularly preferably a linking group composed of one or more atoms selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a germanium atom, and a phosphorus atom. A group selected from the linking group group (I) is particularly preferred.

The linking group group (I) will be described.
In the linking group group (I), R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a substituent. When R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ represent a substituent, the substituent is the same as those described above for Q ₁ , Q ₂ , and Q _3. The atomic group forming the saturated ring has the same meaning as the substituent described in the case of having a substituent. When R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ can be substituted, they may further have a substituent, and R ₄ and R ₅ , R ₆ and R 11 ₇ , R ₈ and R ₉ may be bonded to each other to form a ring, or may be further bonded to an atomic group constituting Q ₁ , Q ₂ or Q ₃ to form a ring. When R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R _10, and R ₁₁ represent a substituent, examples of the substituent are described in Q ₁ , Q ₂ , and Q _{3 above} . The group of atoms forming the unsaturated ring has the same meaning as the example of the substituent explained in the case of having a substituent.

A ₁ is preferably selected from the linking group group (I), of which —C (R ₄ ) (R ₅ ) —, —Si (R ₆ ) (R ₇ ) —, —N ( R ₁₀ ) —, —O—, —S— or —CO—, and more preferably —C (R ₄ ) (R ₅ ) —, —Si (R ₆ ) (R ₇ ) —, It is the case of representing —O— or —S—, and more preferably the case of representing —C (R ₄ ) (R ₅ ) — or —O—.

When A ₁ represents —C (R ₄ ) (R ₅ ) —, R ₄ and R ₅ are preferably an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an amino group, an alkylthio group, or an arylthio group. , An alkyloxy group, an aryloxy group, a hydroxy group, a mercapto group, and a halogen atom. Preferable examples of these groups are the same as those described for the substituent, and more preferable are alkyl groups, cycloalkyl groups, aryl groups, halogen atoms, alkylthio groups, arylthio groups, alkyloxy groups, aryloxy groups. Group, a halogen atom, and more preferably an alkyl group or an aryl group. When these substituents can be further substituted, they can have a substituent.

When A ₁ represents —Si (R ₆ ) (R ₇ ) —, R ₆ and R ₇ are preferably an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an amino group, an alkylthio group, an arylthio group, An alkyloxy group, an aryloxy group, a hydroxy group, a mercapto group, and a halogen atom; Preferable examples of these groups are the same as those described for the substituent, and more preferable are alkyl groups, cycloalkyl groups, aryl groups, halogen atoms, alkylthio groups, arylthio groups, alkyloxy groups, aryloxy groups. Group, a halogen atom, and more preferably an alkyl group or an aryl group. When these substituents can be further substituted, they can have a substituent.

When A ₁ represents —N (R ₁₀ ) —, R ₁₀ is preferably an alkyl group, a cycloalkyl group, or an aryl group. Preferable examples of these groups are the same as the preferable groups described for the substituent, more preferably an alkyl group and an aryl group, and still more preferably an aryl group. When these substituents can be further substituted, they can have a substituent.

In the general formula (I), B ₁ , B ₂ and B ₃ each independently represent a linking group or a single bond. However, when X represents a substituted or unsubstituted aryl group, both B ₁ and B ₃ are not a single bond.
B ₁ is preferably a group selected from the linking group group (I) or a single bond, and more preferably —C (R ₄ ) (R ₅ ) —, —N (R ₁₀ )-, -O-, -S-, -CO- or a single bond, more preferably -O- or a single bond. In the case where B ₁ represents —C (R ₄ ) (R ₅ ) —, —Si (R ₆ ) (R ₇ ) — or —N (R ₁₀ ) —, preferred examples thereof are described in the above A ₁ . Preferred meanings are the same as -C (R ₄ ) (R ₅ )-, -Si (R ₆ ) (R ₇ )-and -N (R ₁₀ )-.

B ₂ and B ₃ are preferably each independently a group selected from the linking group group (I) or a single bond, more preferably —C (R ₄ ) (R ₅ ) —, In this case, —O—, —S—, —SO—, —SO ₂ —, —CO— or a single bond is represented, more preferably —O—, —CO— or a single bond. When B ₂ and B ₃ represent —C (R ₄ ) (R ₅ ) —, —Si (R ₆ ) (R ₇ ) —, or —N (R ₁₀ ) —, preferred examples thereof include the above A _It represents the same meaning as the preferable —C (R ₄ ) (R ₅ ) —, —Si (R ₆ ) (R ₇ ) — and —N (R ₁₀ ) — described in 1.

Said m and n represent 0 or 1 each independently. However, m and n are not both 1, and the compound represented by the general formula (I) does not form a complete cyclic compound centered on a platinum atom. When m or n is 0, X represents an unsaturated ring formed with Q ₂ and a nitrogen atom, or an unsaturated ring formed with Q ₃ and a nitrogen atom, and X is not bonded. To do. More preferably, one of m and n is 1.

Said X represents the partial structure containing the atom couple | bonded with a platinum atom.
The partial structure represented by X includes a group bonded to a platinum atom by a carbon atom, a group bonded to a platinum atom by a nitrogen atom, a group bonded to a platinum atom by a silicon atom, and a group bonded to a platinum atom by a phosphorus atom. A group bonded to a platinum atom by an oxygen atom, or a group bonded to a platinum atom by a sulfur atom, more preferably a group bonded to a platinum atom by a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, a sulfur atom, A group bonded to a platinum atom by a nitrogen atom or an oxygen atom is more preferable, and a group bonded to a platinum atom by an oxygen atom is particularly preferable.

  Examples of the group bonded to the platinum atom by the carbon atom include a substituted or unsubstituted aryl group bonded to the platinum atom by a carbon atom, a substituted or unsubstituted 5-membered heteroaryl group bonded to the platinum atom by a carbon atom, or A substituted or unsubstituted 6-membered heteroaryl group bonded to a platinum atom with a carbon atom is preferred, and a substituted aryl group bonded to a platinum atom with a carbon atom is particularly preferred.

  The group bonded by the oxygen atom is preferably a substituted or unsubstituted hydroxyl group or a substituted or unsubstituted carboxyl group, and more preferably a substituted or unsubstituted carboxyl group.

  The group bonded by the nitrogen atom is preferably a substituted amino group or a nitrogen-containing hetero five-membered heteroaryl group bonded by a nitrogen atom, more preferably a nitrogen-containing hetero five-membered heteroaryl group bonded by a nitrogen atom. , Substituted carbazole, substituted pyrrole, substituted indole and the like are particularly preferable.

The group bonded by the phosphorus atom is preferably a substituted phosphino group. As the group bonded by a silicon atom, a substituted silyl group is preferable.
The group bonded by the sulfur atom is preferably a thiol group or a substituted thiol group.

Next, a preferable range of the general formula (I) will be described.
In the general formula (I), preferably, the unsaturated ring formed together with Q ₁ and the carbon atom is a six-membered ring, and the unsaturated ring formed together with the nitrogen atom and Q ₂ and the nitrogen atom and Q ₃ Are each a six-membered ring, or an unsaturated ring formed with Q ₁ and a carbon atom is a six-membered ring, and an unsaturated ring formed with a nitrogen atom and Q ₂ and a nitrogen atom and Q ₃ Are five-membered rings.

Next, a more preferable range of the general formula (I) will be described.
The general formula (I) more preferably represents a compound represented by the general formula (II) or a compound represented by the general formula (III).

The general formula (II) will be described in detail below.
In the general formula (II), in the formula, R ₁ , R ₂ and R ₃ each independently represent a substituent. Examples of the substituent include, in the general formula (I), the substituent described in the case where the atomic group forming the unsaturated ring described in Q ₁ , Q ₂ , and Q ₃ has a substituent. Represents the same meaning. When R ₁ , R ₂ and R ₃ can be further substituted, they may have a substituent.
R ₁ is preferably an alkyl group, cycloalkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, hetero Ring thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic group, silyl group . Preferred examples of these groups are the same as the preferred groups described for the substituent, more preferably an alkyl group, an aryl group, a sulfonyl group, a halogen atom, a cyano group, a nitro group, and a heterocyclic group, Preferably, they are an alkyl group, an aryl group, a halogen atom, and a cyano group. When these substituents can be further substituted, they can have a substituent.

R ₂ and R ₃ are preferably an alkyl group, a cycloalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfonylamino group, Sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro A group, a sulfino group, a heterocyclic group, and a silyl group. Preferable examples of these groups are the same as the preferable groups described for the substituent, and more preferable are an alkyl group, a cycloalkyl group, an amino group, an aryl group, a heterocyclic group, an alkoxy group, and an aryloxy group. More preferably, R ₂ and R ₃ are an alkyl group, an alkoxy group, or an amino group. When these substituents can be further substituted, they can have a substituent.

P ₁ , p ₂ and p ₃ each independently represents an integer of 0 to 3. When each of p _{1 to} p ₃ is 2 or more, a plurality of R ₁ , R ₂ and R ₃ may be the same or different, and R ₁ , R ₂ , R ₃ , R ₁ and R ₂ , R ₁ and R ₃ , or R ₂ and R ₃ may be bonded to each other to form a ring. Preferably p _1, p ₂ and p ₃ is 0 to 2, more preferably 0-1.

Wherein _{A 1, B 1, B 2} , B 3, m, n and X are the A ₁ in the general formula _{(I), B 1, B} 2, B 3, m, represents the same meaning as n and X. Preferable examples thereof have the same meanings as preferable A ₁ , B ₁ , B ₂ , B ₃ , m, n and X described in the general formula (I).

Next, the general formula (III) will be described.
In Formula _{(III), A 1, B} 2, B 3, m, n and X have the same meanings as _{A 1, B 2, B 3} , m, n and X in the general formula (I) . As preferred examples thereof, the same meanings as preferred A ₁ , B ₂ , B ₃ , m, n and X described in the general formula (I) are represented. _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). Preferable examples thereof represent the same meaning as preferable R ₁ , R ₂ , R ₃ , p ₁ , p ₂ and p ₃ described in the general formula (II).

Next, a more preferable range of the general formula (I) will be described.
The general formula (I) more preferably represents a compound represented by the following general formula (IV) or a compound represented by the following general formula (V).

Next, the general formula (IV) will be described.
In the general formula (IV), A ₁ and B ₁ represent the same meaning as A ₁ and B ₁ in the general formula (I). Preferable examples thereof have the same meanings as preferable A ₁ and B ₁ described in the general formula (I). _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). Preferable examples thereof represent the same meaning as preferable R ₁ , R ₂ , R ₃ , p ₁ , p ₂ and p ₃ described in the general formula (II).

Next, the general formula (V) will be described.
In the general formula (V), A ₁ represents the same meaning as A ₁ in the general formula (I). As a preferable example thereof, the same meaning as the preferable A ₁ described in the general formula (I) is represented. _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). Preferable examples thereof represent the same meaning as preferable R ₁ , R ₂ , R ₃ , p ₁ , p ₂ and p ₃ described in the general formula (II).

  The compound represented by the general formula (I) of the present invention may be a low molecular compound, and an oligomer compound or a polymer compound (weight average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 2000 1000000, more preferably 3000-100000). In the case of a polymer compound, the structure represented by the general formula (1) may be included in the polymer main chain, or may be included in the polymer side chain. In the case of a polymer compound, it may be a homopolymer compound or a copolymer. The compound represented by the general formula (I) of the present invention is preferably a low molecular compound.

  The compound represented by the general formula (I) of the present invention can be applied to an organic EL device, and can be used for any of an electron transport material, a hole block material, an electron block material, and an exciton block material. Are preferably a hole injection material, a hole transport material, an electron block material, and a light emitting material, more preferably a hole injection material and a light emitting material, and still more preferably a light emitting material. When used as a light emitting material, it may be ultraviolet light emission, visible light light emission, or infrared light emission, and may be fluorescent light emission or phosphorescence light emission.

  Next, although the compound example of the compound of this invention is shown, this invention is not limited to this.

  The compound represented by the general formula (I) of the present invention can be synthesized by various known methods. For example, a ligand or a compound containing a dissociated product thereof and a platinum ion is used as a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, In the presence or absence of a solvent such as sulfone solvent, sulfoxide solvent, water, etc., a base (a variety of inorganic and organic bases such as sodium methoxide, t-butoxy potassium, triethylamine, potassium carbonate, etc.) Or in the absence of a base, at room temperature or below or heating (in addition to normal heating, a method using a mantle heater, a method of heating with a microwave, etc. is also effective).

  The reaction time for synthesizing the compound represented by the general formula (I) of the present invention varies depending on the activity of the reaction and is not particularly limited. However, from the viewpoint of improving the yield, it is preferably 1 minute or more and 5 days or less. It is more preferably from 3 minutes to 3 days, and further preferably from 10 minutes to 24 hours.

The reaction temperature for synthesizing the compound represented by the general formula (I) of the present invention varies depending on the activity of the reaction and is not particularly limited. However, from the viewpoint of improving the yield, 0 ° C. or more and 300 ° C. or less are preferable. More preferably, the temperature is more than 150 ° C and less than 250 ° C, and more preferably more than 10 ° C and less than 200 ° C.

Among the compounds represented by the general formula (I) of the present invention, the ligand forming the partial structure of the target complex is preferably 0.1 equivalent to 10 equivalents, more preferably relative to the platinum compound. It can be synthesized by adding 0.3 to 6 equivalents, more preferably 0.5 to 4 equivalents.
Examples of the platinum compound include halides (for example, platinum chloride, potassium chloroplatinate), carboxylates (for example, platinum acetate), diketonates (for example, platinum acetylacetonate), and organic ligands. Examples thereof include platinum compounds (such as dichlorocyclooctadienyl platinum) or hydrates thereof.

  Next, although the specific synthesis example of exemplary compound (1) is shown among the compounds represented by the said general formula (I) of this invention, it is not limited to this method.

6-bromopicolinic acid <1> 3.0 g (0.015 mol), t-butyl alcohol 30 g, and pyridine 9.0 ml (0.045 mol) are added to a 100 ml three-necked flask and stirred under ice cooling. Then, 5.0 g (0.026 mol) of p-toluenesulfonyl chloride was added, and the mixture was further stirred for 1 hour under ice cooling, and then gradually warmed to room temperature. Water was added to the reaction mixture to precipitate crude crystals, which were filtered off. The crude crystals were dissolved in ethyl acetate and dried over anhydrous magnesium sulfate, and the inorganic salt was filtered. The obtained filtrate was concentrated by a rotary evaporator. The obtained crystals were dispersed and washed with hexane to obtain Compound <2> in a yield of 3.02 g (79%).
¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.97 (dd, J = 1.2, 6.8 Hz, 1H), 7.65 (t, J = 8.0 Hz, 1H), 7.62 ( dd, J = 1.6, 7.6 Hz, 1H), 1.62 (s, 9H).

In a 500 ml three-necked flask, resorcinol <3> 89 g (0.81 mol), 2-bromopyridine 64.0 g (0.405 mol), N, N-dimethylacetamide 168 ml, potassium carbonate 168 g (1.22 mol). The mixture was added and heated and stirred with a mechanical stirrer for 8 hours. The reaction mixture was neutralized with water and 10% diluted hydrochloric acid, and the aqueous layer was extracted three times with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure using a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 8.3 g of compound <4> in a yield of 11%.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 8.19 (dd, J = 1.2, 4.8 Hz, 1H), 7.71 (ddd, J = 2.0, 7.2, 8.0 Hz) , 1H), 7.22 (t, J = 8.0 Hz, 1H), 6.98-7.05 (m, 2H), 6.94 (br.d, J = 8.4 Hz, 1H), 6 .60-6.66 (m, 2H), 6.55 (br.t, J = 2 Hz, 1H).

In a 100 ml three-necked flask, compound <4> 0.940 g (5.02 mmol), compound <2> 1.08 g (5.51 mmol), N, N-dimethylacetamide 18 ml, potassium carbonate 2.12 g (15.15 mmol). 3 mmol), and the mixture was stirred with heating at 140 ° C. for 12 hours. After adding water to the reaction mixture, the aqueous layer was extracted three times with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, inorganic salts were filtered, and the obtained filtrate was concentrated by a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 0.25 g (14%) of compound <5>.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 8.21 (br.dd, J = 1.6, 5.2 Hz, 1H), 7.77 (s, 1H), 7.76 (d, J = 1.6 Hz, 1H), 7.69 (br.ddd, J = 2.0, 7.2, 8.0 Hz, 1H), 7.40 (t, J = 8.4 Hz, 1H), 6.97. -7.10 (m, 5H), 6.94 (d, J = 8.4 Hz, 1H), 1.59 (s, 9H).

A 100 ml three-necked flask was charged with 136 mg (mmol) of compound <5>, 5.0 ml of tetrahydrofuran and 0.2 ml of trifluoroacetic acid, and heated and stirred at 80 ° C. for 8 hours. The reaction mixture was directly concentrated under reduced pressure to give 109 mg of pale yellow oily compound <6>. This compound <6> was immediately used for the next step without further purification.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 8.42 (br.d, J = 4.0 Hz, 1H), 8.06 (m, 1H), 7.98 (d, J = 1.6 Hz, 1H), 7.97 (s, 1H), 7.54 (t, J = 8.4 Hz, 1H), 7.33 (br.t, J = 6.4 Hz, 1H), 7.25-7. 30 (m, 1H), 7.05-7.18 (m, 3H), 7.02 (br.t, 2.4 Hz, 1H).

To a 100 ml three-necked flask, compound <6> 109 mg, potassium chloroplatinate 147 mg (0.354 mmol), acetonitrile 30 ml and water 10 ml were added and heated under reflux for 15 hours under a nitrogen stream. Water was added to the reaction mixture, and the resulting yellow crystals were filtered off and washed with acetonitrile and water. The obtained crude crystals were purified by silica gel column chromatography (eluent: chloroholom) to obtain 19 mg (10%, 2 steps) of Exemplified Compound (1) of the present invention.
¹ H-NMR (400 MHz, CDCl ₃ ) δ = 9.44 (dd, J = 2.4, 6.0 Hz, 1H), 8.08 (dd, J = 7.6, 8.8 Hz, 1H), 7.94 (dt, J = 1.6, 8.0 Hz, 1H), 7.86 (dd, J = 1.2, 6.0 Hz, 1H), 7.34 (dd, J = 0.8, 8.4 Hz, 1H), 7.20-7.25 (m, 2H), 7.04-7.08 (m, 1H), 7.04 (dd, J = 1.2, 8.0 Hz, 1H) ), 6.99 (dd, J = 1.2, 6.8 Hz, 1H).
Exemplified compound (1) of the present invention exhibited an emission maximum in a dichloromethane solution at 480 nm at room temperature and at 468 nm under liquid nitrogen cooling conditions.

Next, the light emitting device containing the compound represented by the general formula (I) of the present invention will be described.
The light-emitting device of the present invention can be used in ordinary light-emitting systems, driving methods, usage forms, and the like except that it is a device that uses the compound represented by the general formula (I) of the present invention.

  The light-emitting element of the present invention can improve the light extraction efficiency by various known methods. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.

The external quantum efficiency of the light emitting device of the present invention is preferably 5% or more, more preferably 10% or more, and further preferably 13% or more.
The maximum value of the external quantum efficiency when numeric external quantum efficiency of the device is driven at 20 ° C., or around 100~300cd / m ² when the device is driven at 20 ° C. (preferably 200~300cd / m ²⁾ The value of external quantum efficiency at can be used.
As the numerical value of the external quantum efficiency in the present invention, the maximum value of the external quantum efficiency when the element is driven at 20 ° C. is adopted as the value.
In the present invention, using a source measure unit type 2400 manufactured by Toyo Technica, a DC constant voltage is applied to the EL element to emit light, and the luminance is measured using a luminance meter BM-8 manufactured by Topcon Corporation, and is 200 cd / m ^2. The external quantum efficiency at can be calculated.
Specifically, the external quantum efficiency of the device is calculated from the result and the luminous efficiency curve obtained by measuring the emission luminance, emission spectrum, and current density. That is, the number of input electrons can be calculated using the current density value. The emission luminance was converted to the number of photons emitted by integral calculation using the emission spectrum and the relative visibility curve (spectrum). From these, the external quantum efficiency (%) is calculated by “(number of photons emitted / number of electrons input to the device) × 100”.

  The emission spectrum can be measured using a multi-channel analyzer PMA-11 manufactured by Hamamatsu Photonics.

Further, the internal quantum efficiency of the light emitting device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. The internal quantum efficiency of the device is calculated by “internal quantum efficiency = external quantum efficiency / light extraction efficiency”.
In a normal organic EL element, the light extraction efficiency is about 20%. However, the shape of the substrate, the shape of the electrode, the thickness of the organic layer, the thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.

  The light-emitting element of the present invention may be a so-called top emission method (described in Japanese Patent Application Laid-Open Nos. 2003-208109, 2003-248441, 2003-257651, 2003-282261, etc.) in which light emission is extracted from the cathode side.

  The driving durability of the light emitting device of the present invention is determined by applying a direct current voltage to the organic EL device to emit light using, for example, a source measure unit type 2400 manufactured by Toyo Technica Co., Ltd. It can be evaluated by measuring using BM-8 and measuring the time until the initial luminance is halved (luminance half time).

  The case where the compound represented by the general formula (I) of the present invention is used as a light emitting material is preferable. When used as a light emitting material, ultraviolet light emission or infrared light emission may be used, and fluorescence light emission or phosphorescence light emission may be used. An organic EL (electroluminescence) element can be mentioned as a typical light emitting element.

[Organic electroluminescence device]
Hereinafter, the organic electroluminescent element of the present invention (hereinafter sometimes referred to as “organic EL element” as appropriate) will be described in detail.
The light-emitting element of the present invention has a cathode and an anode on a substrate, and an organic compound layer including an organic light-emitting layer (hereinafter sometimes simply referred to as “light-emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  As an aspect of lamination of the organic layer (organic compound layer) in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic compound layer.
Specific examples thereof include zirconia stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Organic materials such as norbornene resin and poly (chlorotrifluoroethylene).
For example, when glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

  There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.

  The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the organic light emitting layer.

The substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.
As a material for the moisture permeation preventive layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method.
When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.

<Anode>
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually preferably provided as a transparent anode.

Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof.
Specific examples of anode materials include conductive metals such as tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony and fluorine. Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the organic electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element, but it is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching using a laser or the like. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is described in detail in Yutaka Sawada's “New Development of Transparent Conductive Film” published by CMC (1999), and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say.

  The cathode materials are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these publications can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

<Organic layer>
The organic layer (hereinafter also referred to as “organic compound layer”) in the present invention will be described.
The organic electroluminescent element of the present invention has at least one organic compound layer including a light emitting layer (hereinafter also referred to as “organic light emitting layer”) between a pair of electrodes. Examples of the organic compound layer include a hole transport layer, an electron transport layer, a charge blocking layer, a hole injection layer, and an electron injection layer as described above.

-Formation of organic compound layer-
In the organic electroluminescent element of the present invention, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

-Light emitting layer (organic light emitting layer)-
The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide and to emit light.
The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the light emitting material (dopant) may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of fluorescent light-emitting materials that can be used in combination with the compound represented by the general formula (I) of the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene. Derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridines Derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolino Various metal complexes represented by metal complexes of the metal complex and pyrromethene derivatives of derivatives, polythiophene, polyphenylene, polyphenylene-vinylene and the like of the polymer compound include compounds such as organic silane derivatives.

Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H.C. Examples include ligands described in Yersin's "Photochemistry and Photophysics of Coordination Compounds" published by Springer-Verlag 1987, Akio Yamamoto "Organic Metal Chemistry-Fundamentals and Applications-" .
Specific ligands are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketones Ligand (for example, acetylacetone), carboxylic acid ligand (for example, acetic acid ligand), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing Heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  Examples of phosphorescent materials that can be used in combination with the compound represented by the general formula (I) of the present invention include, for example, US 6303231 B1, US 6097147, WO 00/57676, WO 00/70655, WO 01/39234, WO 01/41512 A1, WO 02/02714 A2, WO 02/15645 A1, JP 2001-247659, EP 12112257, JP 2002-226495, JP 2002-234894, JP 2001247478, JP 2001-298470 Patent Documents such as JP2002-173675, JP2002-203678, and JP2002-203679, Nature 395, 151 (1998), Applied Physics Letters, 75, 4 (19). 9), Polymer Preprints, 41, 770 (2000), Journal of American Chemical Society, 123, 4304 (2001), Applied Physics Letters, 79, 2082 (1999), etc. Those described in the literature can be suitably used.

  When the compound represented by the general formula (I) is used as a light emitting material, the light emitting material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by weight, and 0.5 to 20% by weight. More preferably.

Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.
The host material is preferably contained in the light emitting layer in an amount of 50 to 99.9% by mass, and more preferably 70 to 99.8% by mass.
The ratio of the light emitting material to the host material in the light emitting layer is not particularly limited, but among them, the range of 0.1: 99.9 to 40:60 is preferable from the viewpoint of light emission efficiency and durability, and 0.2: 99. The range of 0.8-20: 80 is more preferable, and the range of 0.5: 99.5-10: 90 is particularly preferable.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.
The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and still more preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<Protective layer>
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerization of a copolymer having a cyclic structure in the copolymer main chain. Copolymer, 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like.

  The method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

<Sealing>
Furthermore, the organic electroluminescent element of this invention may seal the whole element using a sealing container.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Obtainable.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6023308, and the like can be applied.

  Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.

(Comparative Example 1)
The cleaned ITO substrate is put in a vapor deposition apparatus, and the following NPD is vapor-deposited by 50 nm, and the following CBP and the following compound 1-1 ′ (compound described in Non-Patent Document 1) are vapor-deposited by 40 nm at a mass ratio of 10: 1. Further, 10 nm of BAlq was further deposited thereon, and 30 nm of Alq was further deposited thereon. A patterned mask (with a light emitting area of 4 mm × 5 mm) was placed on the obtained organic thin film, lithium fluoride was deposited by 3 nm, and then aluminum was deposited by 60 nm to produce an organic EL device.
Although a direct current voltage (5 V) was applied to the obtained organic EL device, no luminescence was detected.

(Comparative Example 2)
In Comparative Example 1, an organic EL device was produced in the same manner as in Comparative Example 1 except that Compound 1-2 ′ described in International Publication No. 2004-039914 pamphlet was used instead of Compound 1-1 ′.
When a DC constant voltage (5 V) was applied to the obtained organic EL device, light emission was observed for 10 hours at a luminance of 300 cd / m ² .

Example 1
In Comparative Example 1, an organic EL device was produced in the same manner as in Comparative Example 1 except that Compound (I) of the present invention was used instead of 1-1 ′.
When a DC constant voltage (5 V) was applied to the obtained organic EL element, light emission was observed. When light was emitted for 10 hours at a luminance of 300 cd / m ² , the durability was better than that of Comparative Example 2.

Similarly, even when the compound represented by the general formula (I) of the present invention is used, an organic light emitting device having excellent light emitting performance and high durability can be produced. Further, the compound of the present invention can emit blue to green phosphorescence, and a blue to green light emitting element can be produced by containing the compound of the present invention.
The light emitting device of the present invention can be suitably used in the fields of display devices, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like. The compounds of the present invention can also be used in medical applications, fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, recording media materials, inkjet pigments, dyes for color filters, color conversion filters, analytical applications, etc. Applicable.

Claims (6)

An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein the organic layer contains at least one compound represented by the following general formula (I) in the organic layer Electroluminescent device.

[Wherein, Q ₁ represents an atomic group necessary for forming an unsaturated ring together with a carbon atom. Q ₂ and Q ₃ each independently represents an atomic group necessary for forming an unsaturated ring together with a nitrogen atom. X represents a partial structure containing an atom bonded to a platinum atom.
A ₁ represents a linking group, and B ₁ , B ₂ and B ₃ each independently represent a linking group or a single bond. However, when X represents a substituted or unsubstituted aryl group, both B ₁ and B ₃ are not a single bond. m and n each independently represents 0 or 1. However, m and n are not both 1. When m or n is 0, an unsaturated ring formed with Q ₂ and a nitrogen atom, or an unsaturated ring formed with Q ₃ and a nitrogen atom, and X means that they are not bonded. To do. ] The organic electroluminescent element according to claim 1, wherein the general formula (I) is represented by the following general formula (II).

[Wherein, R ₁ , R ₂ and R ₃ each independently represents a substituent. p _1, p ₂ and p ₃ each independently represent an integer of 0-3. _{A 1, B 1, B 2} , B 3, m, n and X have the same meanings as _{A 1, B 1, B 2} , B 3, m, n and X in the general formula (I). ] The organic electroluminescent element according to claim 1, wherein the general formula (I) is represented by the following general formula (III).

[Wherein R ₁ , R ₂ , R ₃ , p ₁ , p ₂ and p ₃ represent the same meaning in R ₁ , R ₂ , R ₃ , p ₁ , p ₂ and p ₃ in the general formula (II) . _{A 1, B 2, B 3} , m, n and X have the same meanings as _{A 1, B 2, B 3} , m, n and X in the general formula (I). ] The organic electroluminescent element according to claim 1, wherein the general formula (I) is represented by the following general formula (IV).

[Wherein, A ₁ and B ₁ represent the same meaning as A ₁ and B ₁ in formula (I). _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). ] The organic electroluminescent element according to claim 1, wherein the general formula (I) is represented by the following general formula (V).

[Wherein, A ₁ represents the same meaning as A ₁ in formula (I). _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). ] The organic electroluminescent element according to claim 1, wherein the general formula (I) is represented by the following general formula (VI).

[Wherein A ₁ , B ₁ , B ₂ , B ₃ , m, n and X have the same meaning as A ₁ , B ₁ , B ₂ , B ₃ , m, n and X in the general formula (I) To express. _{R 1, R 2, R 3} , p 1, p 2 and p ₃ are as defined _{R 1, R 2, R 3} , p 1, p 2 and p ₃ in the general formula (II). ]